WO2013137411A1 - Particules de mousse en résine polypropylène, corps moulé en mousse dans le moule comprenant des particules de mousse en résine polypropylène, et procédé de production - Google Patents

Particules de mousse en résine polypropylène, corps moulé en mousse dans le moule comprenant des particules de mousse en résine polypropylène, et procédé de production Download PDF

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WO2013137411A1
WO2013137411A1 PCT/JP2013/057267 JP2013057267W WO2013137411A1 WO 2013137411 A1 WO2013137411 A1 WO 2013137411A1 JP 2013057267 W JP2013057267 W JP 2013057267W WO 2013137411 A1 WO2013137411 A1 WO 2013137411A1
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polypropylene resin
diethanolamine
particles
aliphatic
weight
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PCT/JP2013/057267
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English (en)
Japanese (ja)
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圭志 佐藤
清敬 中山
吉田　融
孝元 海老名
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株式会社カネカ
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Priority to US14/384,590 priority Critical patent/US20150025162A1/en
Priority to EP13760551.5A priority patent/EP2826813B1/fr
Priority to CN201380014019.5A priority patent/CN104245809B/zh
Priority to JP2014505007A priority patent/JP5976098B2/ja
Publication of WO2013137411A1 publication Critical patent/WO2013137411A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0028—Use of organic additives containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • B29C44/3446—Feeding the blowing agent
    • B29C44/3453—Feeding the blowing agent to solid plastic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3461—Making or treating expandable particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/36—Feeding the material to be shaped
    • B29C44/38—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length
    • B29C44/44—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form
    • B29C44/445—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form in the form of expandable granules, particles or beads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3415—Heating or cooling
    • B29C44/3426—Heating by introducing steam in the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/034—Post-expanding of foam beads or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/14—Copolymers of propene

Definitions

  • the present invention relates to polypropylene resin foam particles, in-mold foam moldings comprising the polypropylene resin foam particles, and methods for producing them. More specifically, the present invention relates to a polypropylene resin foamed particle capable of reducing variation in antistatic performance at a plurality of portions of one in-mold foam molded product, and an in-mold foam molded product comprising the polypropylene resin foamed particle.
  • Polypropylene-based resin foam moldings are excellent in physical properties such as buffering properties and heat insulation properties, and are therefore used in various fields such as packaging materials, cushioning materials, heat insulating materials, and building materials.
  • the in-mold foam molding method in which polypropylene resin foam particles are filled in a mold and heated with water vapor or the like to fuse the foam particles together to obtain a foam with a predetermined shape is relatively difficult to produce products with complex shapes. Since it can be easily obtained, it is used in many applications.
  • shock absorbing packaging materials for electronic parts and machine parts such as OA equipment may be disgusting with dust and static electricity.
  • Polypropylene resin foam particles with antistatic performance for such cases An in-mold foam molded body is used.
  • a method for imparting antistatic performance to an in-mold foam molded product a method of applying a surfactant to the surface of the in-mold foam molded product or a method using a foam particle in which a surfactant is previously kneaded into a mold is used.
  • a typical method is to produce an inner foam molded article.
  • the method of producing an in-mold foam molded product from foamed particles in which a surfactant has been kneaded in advance in the resin is more antistatic than the method of applying a surfactant to the surface of the in-mold foam molded product. It is often used because it is excellent and the working method is easy to simplify.
  • the polypropylene resin expanded particles having antistatic performance contain 0.1 to 5% by weight of a nonionic surfactant having an average molecular weight of 200 to 1000 having antistatic performance, and have a DSC curve obtained by differential scanning calorimetry.
  • a technique related to polypropylene resin expanded particles in which a high temperature side calorific value peak of 10 to 30 J / g appears is disclosed (for example, Patent Document 1).
  • a technique relating to polypropylene resin foam particles produced through an aqueous dispersion using an inorganic dispersant containing 0.05 to 5 parts by weight of an antistatic agent for example, Patent Document 2 and 3).
  • Patent Documents 1 to 3 N, N- (2-hydroxyethyl) alkylamine, stearyl diethanolamine monostearate, hydroxyalkyl monoethanolamine, glycerin is used as an antistatic agent or a surfactant capable of imparting antistatic performance.
  • Fatty acid esters and the like are described (note that these are classified as low molecular weight antistatic agents).
  • Patent Document 1 does not describe an aliphatic diethanolamine fatty acid ester.
  • Patent Documents 1 to 3 also mention that these low molecular weight antistatic agents can be used alone, or that different antistatic agents can be used in combination.
  • Patent Documents 1 to 3 there is no specific example in the case of using different types of low molecular weight antistatic agents in combination, and the combined use of different types of low molecular weight antistatic agents is compared with the single use, There is no disclosure about the appearance of excellent properties.
  • Patent Document 4 describes a hydrophilic polymer, part of which corresponds to a polymer-type antistatic agent, for example, a polyether ester amide or a quaternary ammonium base-containing copolymer described in Examples. Etc.
  • Patent Documents 5 and 6 a technique for imparting antistatic performance by using a polymer type antistatic agent alone is also disclosed (for example, Patent Documents 5 and 6).
  • Patent Documents 5 and 6 a technique for imparting antistatic performance by using a polymer type antistatic agent alone.
  • a polymer type antistatic agent alone in order to develop the same antistatic performance as that of the low molecular weight type antistatic agent, it is necessary to add more than 10 times the amount of the low molecular weight type antistatic agent.
  • Patent Document 6 discloses a technique of adding a polymer-type antistatic agent only to a coating layer in a polyolefin resin foamed particle comprising a core layer and a coating layer. In this case, the entire polyolefin resin foamed particle The addition amount of the polymer type antistatic agent in is small.
  • the polyolefin resin foamed particles composed of the core layer and the coating layer require an extruder equipped with a complicated mold in the process of producing the polyolefin resin particles. Thickness control or the like is not easy, and there is a problem that productivity of the polyolefin resin expanded particles is remarkably reduced.
  • Patent Document 7 As a antistatic agent with improved antistatic performance, a technique relating to polyester resin foamed particles in which a different type of antistatic agent is used in combination with a higher alcohol is disclosed (for example, Patent Document 7).
  • Patent Document 8 is a technique that is said to be effective in preventing smoke generation during molding without reducing the antistatic effect and slipping property, but in the case of using an aliphatic diethanolamine fatty acid ester and an aliphatic diethanolamine together. Even if it is not used, there is no description or suggestion of variation in antistatic performance.
  • Patent Document 9 is a technique for reducing film formation defects due to the deposition of volatiles without impairing the antistatic effect and physical / mechanical properties.
  • aliphatic diethanolamine fatty acid ester and aliphatic diethanolamine are used in combination Even if it is not used, there is no description or suggestion of variation in antistatic performance.
  • Patent Document 10 is a technology relating to an agrochemical film that is excellent in anti-fogging property to prevent fogging due to condensed water droplets and does not cause whitening or stickiness due to bleeding of the anti-fogging agent, and includes aliphatic diethanolamine fatty acid ester and aliphatic as anti-fogging agent. There is a description of using diethanolamine together, but there is no description or suggestion of antistatic performance itself.
  • the technology related to the expanded polypropylene resin particles having good antistatic performance or the expanded foamed product in the polypropylene based resin mold is a known technology, but the dispersion of the antistatic performance is suppressed.
  • the technology relating to the foamed particles or the polypropylene resin-in-mold foam-molded product is not yet known.
  • An object of the present invention is to obtain a polypropylene resin foamed particle in which variation in antistatic performance is suppressed, and in a polypropylene resin in-mold foam molded product obtained using the polypropylene resin foamed particle, one mold
  • the object is to suppress variation in antistatic performance at different sites in the inner foam molded body.
  • the present inventors have found that variations in antistatic performance at different parts of one in-mold foam molded product in polypropylene resin expanded particles or polypropylene resin in-mold foam molded products in which variation in antistatic performance is suppressed.
  • the conventional equipment such as an extruder for dispersing the antistatic agent in the polypropylene resin. I found the technology.
  • the present invention includes a polypropylene resin foamed particle, a method for producing a polypropylene resin foam particle, and a method for producing an in-mold foam molded article.
  • the aliphatic diethanolamine fatty acid ester and the aliphatic diethanolamine are contained, and the total content of the aliphatic diethanolamine fatty acid ester and the aliphatic diethanolamine is 0.1 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the polypropylene resin.
  • a polypropylene resin expanded particle comprising the polypropylene resin composition.
  • the manufacturing method of the polypropylene resin expanded particle characterized by consisting of the manufacturing process of following (a) and (b).
  • Step (A) Contains both aliphatic diethanolamine fatty acid ester and aliphatic diethanolamine, and the total content of aliphatic diethanolamine fatty acid ester and aliphatic diethanolamine is 0.1 parts by weight or more with respect to 100 parts by weight of the polypropylene resin
  • Step (b) of producing polypropylene resin particles by melting and kneading a polypropylene resin composition of 5 parts by weight or less with an extruder, extruding into a strand form from the tip of the extruder, and then cutting.
  • Resin particles, water, an inorganic dispersant and a foaming agent are accommodated in a pressure vessel and dispersed under stirring conditions, and after raising the temperature above the softening point temperature of the polypropylene resin particles, the internal pressure of the pressure vessel Discharge the dispersion in the pressure vessel to a low pressure range to produce polypropylene resin.
  • An in-mold foam-molded article characterized by obtaining a mold-in-mold foam-molded article obtained by filling a mold with polypropylene-based resin foam particles comprising a polypropylene-based resin composition having a content of 5 parts by weight or less and heating the mold. Production method.
  • the polypropylene resin foam particles having antistatic performance of the present invention, and the polypropylene resin in-mold foam moldings comprising the polypropylene resin foam particles have little variation in antistatic performance, and in particular, one in-mold foam molding. Variation in antistatic performance at different sites is suppressed.
  • DSC differential scanning calorimetry
  • the measurement locations (numbers 1 to 10) of the surface specific resistance values on the surface of 400 mm long ⁇ 300 mm wide of the in-mold foam molded bodies obtained in Examples and Comparative Examples are shown.
  • the arrangement schematic diagram of a screw pipe and a glass plate in fogging evaluation in an example and a comparative example is shown.
  • the polypropylene resin used in the present invention is not particularly limited, and is a polypropylene homopolymer, ethylene / propylene random copolymer, butene-1 / propylene random copolymer, ethylene / butene-1 / propylene random copolymer, Examples thereof include ethylene / propylene block copolymers, butene-1 / propylene block copolymers, propylene-chlorinated vinyl copolymers, and propylene / maleic anhydride copolymers.
  • an ethylene / propylene random copolymer and an ethylene / butene-1 / propylene random copolymer are preferable because they have good foamability and good moldability.
  • the butene-1 is synonymous with 1-butene.
  • the ethylene content in the ethylene / propylene random copolymer or ethylene / butene-1 / propylene random copolymer is preferably 0.2% by weight or more and 10% by weight or less in 100% by weight of each copolymer.
  • the butene content in the ethylene / butene-1 / propylene random copolymer is preferably 0.2% by weight or more and 10% by weight or less in 100% by weight of the copolymer.
  • the total content of ethylene and butene-1 is preferably 0.5% by weight or more and 10% by weight or less.
  • fusing point of the polypropylene resin used by this invention there is no restriction
  • the melting point of the polypropylene resin is measured by a differential scanning calorimetry method (hereinafter referred to as “DSC method”). Specifically, 5 to 6 mg of the resin is heated at a rate of 10 ° C./min. After the temperature was increased from 40 ° C. to 220 ° C. and melted, the temperature was decreased from 220 ° C. to 40 ° C. and crystallized at a temperature decrease rate of 10 ° C./min, and further at a temperature increase rate of 10 ° C./min. From the DSC curve obtained when the temperature is raised from 40 ° C. to 220 ° C., the melting peak temperature at the second temperature rise can be determined as the melting point.
  • DSC method differential scanning calorimetry method
  • the heat of crystal fusion of the polypropylene resin used in the present invention is not particularly limited, and is preferably 50 J / g or more and 110 J / g or less, more preferably 75 J / g or more and 100 J / g or less, and 85 J / g or more and 95 J / g or less.
  • the heat of crystal fusion is less than 50 J / g, it will be difficult to maintain the shape of the expandable resin particles, and if it exceeds 110 J / g, it will be difficult to increase the expansion ratio.
  • the amount of crystal melting heat is related to the amount of crystal of the polypropylene resin, and the higher the amount of crystal melting heat, the larger the amount of crystal.
  • polypropylene resins with a large amount of crystals inhibit surface migration of the antistatic agent more than polypropylene resins with a small amount of crystals (Reference: Application and Evaluation Technology of Antistatic Materials) Supervised by Yuji Murata, CMC Publishing, 2003). That is, the use of a polypropylene resin having a small amount of crystal is superior in antistatic performance.
  • the heat of crystal fusion of the polypropylene resin was measured by the DSC method. Specifically, 5 mg to 6 mg of the resin was heated from 40 ° C. to 220 ° C. at a temperature rising rate of 10 ° C./min. After being melted, the temperature is lowered from 220 ° C. to 40 ° C. at a rate of 10 ° C./min and crystallized, and then the temperature is further raised from 40 ° C. to 220 ° C. at a rate of 10 ° C./min.
  • the amount of heat can be determined as the amount of heat of crystal melting.
  • the melt index (hereinafter referred to as “MI”) of the polypropylene resin used in the present invention is not particularly limited, but is preferably 3 g / 10 min to 30 g / 10 min, more preferably 4 g / 10 min to 20 g / 10 min. More preferably, it is 5 g / 10 min or more and 18 g / 10 min or less.
  • the MI of the polypropylene resin When the MI of the polypropylene resin is less than 3 g / 10 min, it tends to be difficult to increase the expansion ratio. If the MI of the polypropylene resin exceeds 30 g / 10 min, the bubbles of the obtained polypropylene resin foamed particles are connected, and the compression strength of the polypropylene resin in-mold foam molded product tends to decrease, or the surface property tends to decrease. is there.
  • the MI of the polypropylene resin is in the range of 3 g / 10 min to 30 g / 10 min, it is easy to obtain polypropylene resin expanded particles having a relatively large expansion ratio. Furthermore, the polypropylene resin in-mold foam-molded product obtained by in-mold foam molding of the polypropylene resin foam particles has excellent surface beauty and small dimensional shrinkage.
  • the MI value is an MI measuring instrument described in JIS K7210: 1999, with an orifice of 2.0959 ⁇ 0.005 mm ⁇ , an orifice length of 8.000 ⁇ 0.025 mm, a load of 2160 g, and 230 ⁇ 0.2 ° C. It is the value measured below.
  • the polymerization catalyst for synthesizing the polypropylene resin used in the present invention is not particularly limited, and a Ziegler catalyst, a metallocene catalyst, or the like can be used.
  • the antistatic performance of the obtained polypropylene-based resin foamed particles and in-mold foam-molded articles composed of the polypropylene-based resin foamed particles is used. Variation is suppressed. That is, the problem of the present invention can be solved.
  • the antistatic performance is exhibited, but the variation cannot be suppressed.
  • the total content of aliphatic diethanolamine fatty acid ester and aliphatic diethanolamine is 0.1 to 5 parts by weight with respect to 100 parts by weight of the polypropylene resin, It is more preferably 0.3 parts by weight or more and 3 parts by weight or less, and further preferably 0.5 parts by weight or more and 1.5 parts by weight or less.
  • the antistatic performance tends to be hardly exhibited.
  • the total content exceeds 5 parts by weight, the effect of suppressing variation in antistatic performance is saturated, and the surface of the polypropylene resin foamed particles and the polypropylene resin molded in-mold foam is sticky,
  • polypropylene resin particles are produced using an extruder, which will be described later, the extrusion discharge amount is not stable, and the shape and weight of the obtained polypropylene resin particles tend to vary.
  • the volatilization amount of the aliphatic diethanolamine fatty acid ester and the aliphatic diethanolamine increases, and the contamination (fogging property) may deteriorate.
  • the weight ratio of the aliphatic diethanolamine fatty acid ester to the total weight of the aliphatic diethanolamine fatty acid ester and the aliphatic diethanolamine is not particularly limited as long as the aliphatic diethanolamine fatty acid ester and the aliphatic diethanolamine are used.
  • the total weight of diethanolamine fatty acid ester and aliphatic diethanolamine is 100% by weight, it is preferably 5% by weight to 95% by weight, more preferably 20% by weight to 95% by weight, and more preferably 40% by weight. More preferably, it is 95 weight% or less.
  • the weight ratio of the aliphatic diethanolamine fatty acid ester is 5% by weight or more and 95% by weight or less, variation in antistatic performance can be further reduced.
  • the aliphatic diethanolamine fatty acid ester used in the present invention is not particularly limited, but the antistatic performance of the polypropylene resin foamed particles and the polypropylene resin in-mold foam molding is sufficiently expressed, the surface is not sticky, and the resin is deteriorated. From the viewpoint of not promoting the above, it is preferably a compound represented by the general formula (1).
  • the aliphatic diethanolamine fatty acid ester may be composed of only a single compound having the predetermined R 1 and R 2 , and at least one of R 1 and R 2 may have a plurality of different carbon numbers. It may be a mixture containing a compound.
  • CH 3 , R 2 — (CH 2 ) 16 CH 3 ) is more preferred.
  • the antistatic performance of a polypropylene resin expanded particle and a polypropylene resin-in-mold foam-molding body expresses sufficiently, there is no stickiness of a surface, and deterioration of resin is not promoted. From the viewpoint, the compound represented by the general formula (2) is preferable.
  • aliphatic diethanolamine may be composed of only a single compound having a predetermined R 3, the carbon number of R 3 may be a mixture containing different compounds.
  • aliphatic diethanolamine in the present invention examples include lauryl diethanolamine, myristyl diethanolamine, pentadecyl diethanolamine, palmityl diethanolamine, margaryl diethanolamine, stearyl diethanolamine, arachidyl diethanolamine, behenyl diethanolamine, lignoceryl diethanolamine, and the like. . These may be used alone or in combination of two or more.
  • stearyl diethanolamine has good compatibility with polypropylene resin, and is easy to obtain a synergistic effect with stearyl diethanolamine monostearate, and easily exhibits a variation suppressing effect on antistatic performance.
  • R 3 -(CH 2 ) 17 CH 3 ) is more preferred.
  • the antistatic performance is further improved by further containing 0.001 part by weight or more and 2 parts by weight or less of an aliphatic alcohol with respect to 100 parts by weight of the polypropylene resin.
  • Such an aliphatic alcohol is not particularly limited, but from the viewpoint of low contamination (fogging property), a compound represented by the general formula (3) is preferably used.
  • the aliphatic alcohol may be composed of only a single compound having a predetermined R 4 , or may be a mixture including a plurality of compounds having different R 4 carbon numbers.
  • aliphatic alcohol in the present invention examples include lauryl alcohol, myristyl alcohol, pentadecyl alcohol, palmityl alcohol, margaryl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, and lignoceryl alcohol. These may be used alone or in combination of two or more.
  • aliphatic diethanolamine fatty acid ester and aliphatic diethanolamine, and if necessary, aliphatic alcohol can be masterbatched in advance using the same or different resin as the polypropylene resin that is the main component of the polypropylene resin composition. It is also possible to mix the masterbatch with a polypropylene resin.
  • the aliphatic diethanolamine fatty acid ester, the aliphatic diethanolamine, and, if necessary, the aliphatic alcohol may be mixed in advance before being contained in the polypropylene resin.
  • additives can be added as long as the effects of the present invention are not impaired.
  • organic pigments, antioxidants, light resistance improvers, cell nucleating agents, difficulty A flame retardant, a water absorbing compound, etc. can be mentioned.
  • organic pigment examples include, but are not limited to, perylene-based, polyazo-based, and quinacridone-based organic pigments.
  • the content of the organic pigment is preferably 0.001 part by weight or more and 0.1 part by weight or less with respect to 100 parts by weight of the polypropylene resin from the viewpoint of dispersibility (coloring uniformity) and antistatic performance.
  • the content of the organic pigment exceeds 0.1 parts by weight, the cell diameter of the polypropylene resin foamed particles becomes fine, and the surface property of the polypropylene resin in-mold foam molded product obtained from the polypropylene resin foamed particles is inferior. Tend to get worse.
  • These organic pigments may be masterbatched in advance using the same or different resin as the polypropylene resin as the main component of the polypropylene resin composition, and the masterbatch may be mixed with the polypropylene resin. Is possible.
  • antioxidants examples include, but are not limited to, phenolic antioxidants and phosphorus antioxidants.
  • Examples of the light resistance improver include, but are not limited to, hindered amine light resistance improvers.
  • bubble nucleating agent examples include, but are not limited to, talc, kaolin, barium sulfate, zinc borate, silicon dioxide and the like.
  • flame retardant examples include, but are not limited to, halogen flame retardants, phosphorus flame retardants, hindered amine flame retardants, and the like.
  • the water-absorbing compound examples include substances capable of absorbing water and releasing the absorbed water when foaming to allow water to act as a foaming agent.
  • Specific examples of the water-absorbing compound include, but are not limited to, polyethylene glycol, glycerin, melamine, and the like. Among these water-absorbing compounds, polyethylene glycol is more preferable, and polyethylene glycol having an average molecular weight of 200 to 6000 is most preferable.
  • the polypropylene resin composition in the present invention is usually melt-kneaded in advance using an extruder, kneader, Banbury mixer, roll, etc. so as to be easily used for foaming, and is cylindrical, elliptical, spherical, cubic, rectangular parallelepiped. It is preferable to form polypropylene resin particles that are molded into a desired particle shape such as a cylindrical shape (straw shape).
  • the shape of the polypropylene resin particles is not necessarily the shape of the polypropylene resin expanded particles, and for example, the polypropylene resin particles may shrink in the foaming process. In such a case, a cylindrical or elliptical polypropylene is used. In some cases, spherical polypropylene-based resin expanded particles can be obtained from the resin-based resin particles.
  • polypropylene resin particles from the viewpoint of productivity, it is more preferable to melt-knead with an extruder, extrude into a strand shape from the tip of the extruder, and then cut into polypropylene resin particles.
  • aliphatic diethanolamine fatty acid ester and aliphatic diethanolamine, if necessary, aliphatic alcohol, other additives are usually added to the polypropylene resin before melting or in the process of producing polypropylene resin particles, It is preferable to melt-knead with an extruder. By doing in this way, aliphatic diethanolamine fatty acid ester and aliphatic diethanolamine, aliphatic alcohol as needed, and other additives can be uniformly dispersed in the polypropylene resin.
  • the average particle size of the polypropylene resin particles of the present invention is preferably from 0.1 mm to 10 mm, more preferably from 0.5 mm to 5 mm.
  • the average particle diameter of the polypropylene resin particles is an arithmetic average value of the particle diameters measured for any 20 expanded polypropylene resin particles.
  • the average weight of the polypropylene resin particles of the present invention is preferably from 0.1 mg to 100 mg, more preferably from 0.3 mg to 10 mg.
  • the average weight is an arithmetic average value of the weights of arbitrary ten polypropylene resin expanded particles.
  • the expanded polypropylene resin particles of the present invention can be manufactured as follows.
  • the temperature is raised above the softening point temperature of the polypropylene resin particles. If necessary, hold the temperature after the temperature rise from 0 minutes to 120 minutes or less, and then discharge the dispersion in the pressure vessel to a pressure range lower than the internal pressure of the pressure vessel, to expand the polypropylene resin expanded particles.
  • the pressure range lower than the internal pressure of the pressure vessel is preferably atmospheric pressure.
  • the foaming process is referred to as a “single-stage foaming process”, and the resulting polypropylene-based resin foamed particles are referred to as “single-stage foamed particles”.
  • the dispersion is a mixed liquid in which polypropylene resin particles, an aqueous medium, an inorganic dispersant, a foaming agent, and the like are contained in a pressure vessel and dispersed under stirring conditions.
  • the temperature rise temperature is the melting point of the polypropylene resin ⁇ 20 ° C. or higher, the melting point of the polypropylene resin + 10 ° C. or lower, or the polypropylene resin particles
  • the temperature rise is appropriately determined depending on the type of polypropylene resin used as a raw material, the expansion ratio, the DSC ratio described later, and the like, and needs to be appropriately changed depending on the foaming agent used.
  • the melting point of the polypropylene resin particles was measured by the DSC method. Specifically, 5 to 6 mg of polypropylene resin particles were heated from 40 ° C. to 220 ° C. at a temperature increase rate of 10 ° C./min. After being melted, the temperature is lowered from 220 ° C. to 40 ° C. at a rate of 10 ° C./min and crystallized, and then the temperature is further raised from 40 ° C. to 220 ° C. at a rate of 10 ° C./min. From the obtained DSC curve, the melting peak temperature at the second temperature increase can be determined as the melting point.
  • the pressure range lower than the internal pressure of the pressure vessel is preferably atmospheric pressure.
  • aqueous medium used in the present invention for example, water, alcohol, ethylene glycol, glycerin and the like can be used alone or in combination, but water is preferably used from the viewpoint of foamability, workability or safety. It is most preferable to use water alone.
  • the amount of the aqueous medium used is preferably 50 parts by weight or more and 500 parts by weight or less, and more preferably 100 parts by weight or more and 350 parts by weight or less with respect to 100 parts by weight of the polypropylene resin particles.
  • Examples of the inorganic dispersant used in the present invention include tribasic calcium phosphate, tribasic magnesium phosphate, basic magnesium carbonate, calcium carbonate, basic zinc carbonate, aluminum oxide, iron oxide, titanium oxide, aluminosilicate, Examples include kaolin and barium sulfate. These may be used alone or in combination of two or more. Among these inorganic dispersants, tricalcium phosphate, kaolin, or barium sulfate is preferable from the viewpoint of the stability of the dispersion.
  • a dispersion aid in order to increase the stability of the dispersion in the pressure vessel.
  • the dispersion aid include sodium dodecylbenzenesulfonate, sodium alkanesulfonate, sodium alkylsulfonate, sodium alkyldiphenyl ether disulfonate, sodium ⁇ -olefin sulfonate, and the like. These may be used alone or in combination of two or more.
  • the amount of the inorganic dispersant or dispersion aid used varies depending on the type and the type and amount of polypropylene resin particles used, but the amount of inorganic dispersant used is usually 0 with respect to 100 parts by weight of the aqueous medium.
  • the amount of the dispersion aid is preferably 0.001 part by weight or more and 0.3 part by weight or less.
  • foaming agent used in the present invention examples include organic foaming agents such as propane, normal butane, isobutane, normal pentane, isopentane, hexane, cyclopentane, and cyclobutane, and inorganic foams such as carbon dioxide, water, air, and nitrogen. Agents. These foaming agents may be used alone or in combination of two or more. Among these foaming agents, isobutane and normal butane are more preferable from the viewpoint of easily improving the expansion ratio. Further, from the viewpoint of safety and environmental compatibility, inorganic foaming agents such as carbon dioxide, water, air, and nitrogen are preferable, and a foaming agent containing carbon dioxide is more preferable.
  • organic foaming agents such as propane, normal butane, isobutane, normal pentane, isopentane, hexane, cyclopentane, and cyclobutane
  • inorganic foams such as carbon dioxide, water, air, and nitrogen.
  • the amount of the foaming agent used is not limited, and may be appropriately used according to the desired expansion ratio of the polypropylene resin expanded particles. Usually, the amount is 2 with respect to 100 parts by weight of the polypropylene resin particles. It is preferable that it is not less than 60 parts by weight.
  • water when water is used as the foaming agent, water can be used as an aqueous medium for dispersing the polypropylene resin particles in the pressure resistant container.
  • the polypropylene resin particles when water is used as the foaming agent, can easily absorb the water in the pressure vessel by preliminarily containing the water-absorbing compound in the polypropylene resin particles. Can be easily used as a foaming agent.
  • pressure vessel used in the production of the polypropylene resin expanded particles there is no particular limitation on the pressure vessel used in the production of the polypropylene resin expanded particles, and any pressure vessel that can withstand the pressure in the vessel and the temperature in the vessel may be used.
  • an autoclave type pressure vessel may be mentioned.
  • single-stage foam particles having an expansion ratio of 2 to 35 times are produced, and the single-stage foam particles are placed in a pressure-resistant container, and 0.1 MPa (gauge pressure) or more with nitrogen, air, carbon dioxide, etc.
  • the pressure inside the first-stage expanded particles is made higher than the normal pressure by pressurizing at a pressure of 6 MPa (gauge pressure) or less, and the first-stage expanded particles are further foamed by heating with steam or the like. It is possible to increase.
  • This foaming process is referred to as a “two-stage foaming process”, and the resulting polypropylene resin foamed particles are referred to as “two-stage foamed particles”.
  • the shape of the polypropylene resin foamed particles of the present invention is preferably spherical or substantially spherical in view of the filling property into the mold at the time of in-mold foam molding, but is not limited thereto.
  • a cylindrical shape, an elliptical shape, a rectangular parallelepiped shape, Cylindrical (straw) polypropylene-based resin expanded particles are used.
  • the average diameter (particle diameter) when the polypropylene resin expanded particles are spherical or substantially spherical is not particularly limited, and varies depending on the size of the polypropylene resin particles before expansion, the expansion ratio, and the like. However, 0.5 mm or more and 10 mm or less are preferable, 1 mm or more and 7 mm or less are more preferable, and 2 mm or more and 5 mm or less are more preferable.
  • the average diameter of the expanded polypropylene resin particles is an arithmetic average value of the diameters measured for any 20 expanded polypropylene resin particles.
  • the average diameter of the polypropylene resin foamed particles is less than 0.5 mm, the workability during in-mold foam molding tends to deteriorate, and if it exceeds 10 mm, for example, a molded product having a thin part cannot be produced. There is a tendency for the shape to be limited.
  • the average weight of the polypropylene resin expanded particles is generally the same as that of the polypropylene resin particles, preferably 0.1 mg / particle to 100 mg / particle, and preferably 0.3 mg / particle to 10 mg / particle. More preferred.
  • the average weight is an arithmetic average value of the weights of arbitrary ten polypropylene resin expanded particles.
  • the expansion ratio of the expanded polypropylene resin particles of the present invention is preferably 2 to 60 times, more preferably 3 to 40 times.
  • the expansion ratio here is a true magnification that can be calculated from the density of the polypropylene resin composition before expansion, the weight of the polypropylene resin expanded particles, and the submerged volume.
  • the expanded polypropylene resin particles of the present invention are preferably expanded polypropylene resin particles having two melting peaks in a DSC curve obtained when calorimetric measurement is performed by the DSC method.
  • the melting peak calorie based on the low temperature side melting point is Ql (J / g)
  • the melting peak calorie based on the high temperature side melting point is Qh (J / g)
  • melting based on the high temperature side melting point The ratio of the peak heat quantity to the total heat quantity of melting peak (Qh / (Ql + Qh)) ⁇ 100 (%) (hereinafter sometimes referred to as “DSC ratio”) is preferably 10% to 50%, preferably 15% More preferably, it is 45% or less.
  • DSC ratio is preferably 10% to 50%, preferably 15% More preferably, it is 45% or less.
  • the DSC curve is a curve obtained by heating 5 to 6 mg of polypropylene resin expanded particles from 40 ° C. to 220 ° C. at a temperature increase rate of 10 ° C./min by the DSC method.
  • An example of such a DSC curve is shown in FIG.
  • the melting peak calorie Ql based on the low temperature side melting point is the maximum between (1) the melting peak based on the low temperature side melting point of the DSC curve and (2) the melting peak based on the low temperature side melting point and the melting peak based on the high temperature side melting point. It is the amount of heat surrounded by the tangent line (line segment AB) from the point to the melting start baseline.
  • the melting peak calorie Qh based on the high temperature side melting point is the maximum between (1) the melting peak based on the high temperature side melting point of the DSC curve and (2) the melting peak based on the low temperature side melting point and the melting peak based on the high temperature side melting point.
  • the DSC ratio can be adjusted by changing the temperature rising temperature in the foaming process and the holding time held at the temperature rising temperature after the temperature rising until the dispersion in the pressure vessel is released. For example, if the temperature rise (foaming temperature) is lowered, the DSC ratio tends to increase, and even if the holding time is lengthened. The DSC ratio tends to increase.
  • the polypropylene resin foamed particles of the present invention become a polypropylene resin in-mold foam-molded product by general in-mold foam molding.
  • B) Method to use as it is B) A method of previously injecting an inorganic gas such as air into the foamed particles to impart foaming ability; C) Conventionally known methods, such as a method of filling expanded particles in a mold in a compressed state and molding them, can be used.
  • the polypropylene resin foam particles are filled in a mold that can be closed but cannot be sealed, Fusion foamed polypropylene resin particles are heated for about 3 seconds to 30 seconds with a steam pressure of 0.05 MPa (gauge pressure) or more and 0.5 MPa (gauge pressure) or less using water vapor as a heating medium. Then, after cooling the molding die with water and cooling it to the extent that the deformation of the in-mold foam molding after taking out the in-mold foam molding can be suppressed, the mold is opened to obtain an in-mold foam molding. Can be mentioned.
  • the obtained polypropylene resin in-mold foam-molded product has antistatic performance, and the variation in antistatic performance at a plurality of sites of one in-mold foam-molded product is very small.
  • the present invention includes a polypropylene resin expanded particle, a method for manufacturing a polypropylene resin expanded particle, and a method for manufacturing an in-mold expanded molded article ([1], [8], [11] below). Furthermore, the following [2] to [7], [9], [10], [12] and [13] are included. [1] An aliphatic diethanolamine fatty acid ester and an aliphatic diethanolamine are contained, and the total content of the aliphatic diethanolamine fatty acid ester and the aliphatic diethanolamine is 0.1 to 5 parts by weight with respect to 100 parts by weight of the polypropylene resin.
  • Polypropylene-based resin expanded particles comprising a polypropylene-based resin composition having a part or less.
  • the aliphatic diethanolamine fatty acid ester is a compound represented by the following general formula (1)
  • the aliphatic diethanolamine is a compound represented by the following general formula (2): 1]
  • a method for producing expanded polypropylene resin particles comprising the following production steps (a) and (b): (A) It contains aliphatic diethanolamine fatty acid ester and aliphatic diethanolamine, and the total content of aliphatic diethanolamine fatty acid ester and aliphatic diethanolamine is 0.1 parts by weight or more and 5 parts by weight with respect to 100 parts by weight of polypropylene resin.
  • Step of producing polypropylene resin particles by melt-kneading with an extruder, extruding into a strand form from the tip of the extruder, and then cutting (b) The polypropylene resin particles, water, an inorganic dispersant and a foaming agent After being stored in a pressure vessel and dispersed under stirring conditions, the temperature is raised above the softening point temperature of the polypropylene resin particles, and then the dispersion in the pressure vessel is released to a pressure range lower than the internal pressure of the pressure vessel.
  • the step [9] for producing polypropylene resin expanded particles is characterized in that the heat of crystal melting of the polypropylene resin used in the production step (a) is 85 g / J or more and 95 g / J or less, [8 ] The manufacturing method of the polypropylene resin expanded particle of description. [10] The polypropylene resin composition according to [8] or [9], wherein the polypropylene resin composition in the step (a) is a polypropylene resin composition further containing an aliphatic alcohol. A method for producing expanded particles.
  • An aliphatic diethanolamine fatty acid ester and an aliphatic diethanolamine are contained, and the total content of the aliphatic diethanolamine fatty acid ester and the aliphatic diethanolamine is 0.1 part by weight or more and 5 parts by weight with respect to 100 parts by weight of the polypropylene resin.
  • a method for producing an in-mold foam-molded product comprising filling a mold with polypropylene resin foam particles comprising a polypropylene-based resin composition that is less than or equal to a part and then heating to obtain an in-mold foam-molded product.
  • polypropylene resins and additives used in the examples and comparative examples are as follows.
  • Polypropylene resinPolypropylene resin A [manufactured by Prime Polymer Co., Ltd., F227A]: ethylene / propylene random copolymer having a melting point of 143 ° C., an ethylene content of 3.6% by weight, and MI 7.0 g / 10 min.
  • Resin B [manufactured by Prime Polymer Co., Ltd., E314M]: melting point 145 ° C., ethylene content 3% by weight, butene-1 content 1.5% by weight, MI 5.0 g / 10 min ethylene / butene-1 / propylene random Copolymer
  • Polypropylene resin C [manufactured by Prime Polymer Co., Ltd., prototype]: melting point 148 ° C., ethylene content 1% by weight, butene-1 content 4% by weight, MI 10.0 g / 10 min ethylene / butene- 1 / Propylene random copolymerPolypropylene resin D [manufactured by Prime Polymer Co., Ltd., J105G] Mp 163 °C, MI9.0g / 10 min Propylene homopolymer (2) antistatic agent ⁇ stearyl diethanolamine monostearate [Kao Corporation, electro stripper TS-6B] ⁇ Stearyl diethanolamine [manufact
  • Expansion ratio of polypropylene resin expanded particles d ⁇ v / w (Bulk density of polypropylene resin expanded particles)
  • the polypropylene resin foam particles were gently poured into a 10-liter container having a wide mouth until it overflowed, and then the mouth of the 10 L container was scraped so that the polypropylene resin foam particles became 10 L.
  • the volume was divided by 10 L, and the bulk density was expressed in units of g / L.
  • DSC ratio of polypropylene resin expanded particles Using a differential scanning calorimeter DSC [manufactured by Seiko Instruments Inc .: DSC6200 type], 5-6 mg of polypropylene resin expanded particles are heated from 40 ° C. to 220 ° C. at a temperature rising rate of 10 ° C./min. Got.
  • This DSC curve shows two melting peaks, where Ql (J / g) is the melting peak calorie based on the low-temperature melting point and Qh (J / g) is the melting peak calorie based on the high-temperature melting point.
  • the DSC ratio was determined by the ratio (Qh / (Ql + Qh)) ⁇ 100 (%) of the melting peak heat amount based on the total melting peak heat amount.
  • the weight W (g) of a rectangular parallelepiped in-mold foam molding (length 400 mm x width 300 mm x thickness 50 mm) is measured, and the longitudinal, width, and thickness dimensions of the in-mold foam molding are measured with calipers. From this, the volume V (cm 3 ) was calculated. Next, the value obtained by W / V was converted to the unit g / L to obtain the density of the in-mold foam molded article.
  • the obtained in-mold foam molded product (length 400 mm ⁇ width 300 mm ⁇ thickness 50 mm) was stored in a room at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours, and after adjusting the state, in accordance with JIS-K6911, The measurement was performed using Hiresta MCP-HT201 manufactured by Mitsubishi Yuka Co., Ltd.
  • the surface specific resistance of 10 places shown in FIG. 2 was measured in the surface of length 400mm x width 300mm of one in-mold foaming molding.
  • the following average values and standard deviations were determined together with the minimum and maximum values of the surface specific resistance values at 10 locations.
  • the antistatic performance of the obtained foamed molded product was evaluated according to the following criteria.
  • X The average value of the surface resistivity is 1 ⁇ 10 12 ⁇ or more.
  • the variation in antistatic performance of the obtained foamed molded product was evaluated according to the following criteria.
  • a microscope glass plate (length 76 mm ⁇ width 26 mm ⁇ thickness 1 mm) is placed on the smooth portion (so as to avoid the mold core vent trace portion) of the obtained in-mold foam molding, and the temperature is kept in a constant temperature and humidity chamber. It was left for 72 hours under the conditions of 50 ° C. and relative humidity of 90% (in addition, a 25 g weight was placed on the glass plate to promote contamination during the treatment). Thereafter, the in-mold foam-molded product is taken out, peeled off from the glass plate and naturally dried, and then the state of contamination is observed. Contamination was evaluated according to the following criteria. A: Almost no dirt transferred from the surface of the in-mold foam molded product is seen. ⁇ : Dirt transferred from the surface of the in-mold foam molded product is scattered. X: Dirt transferred from the surface of the in-mold foam molded body is remarkable.
  • the fogging evaluation was performed according to the following criteria. ⁇ : Dirt (cloudy) cannot be confirmed. (Triangle
  • Examples 1 to 23, Comparative Examples 1 to 13 [Production of polypropylene resin particles]
  • the type and amount of polypropylene resin, antistatic agent, aliphatic alcohol, other additives, and 0.01 parts by weight of the organic pigment perylene red shown in Table 1 or Table 2 are mixed and kneaded with a 50 mm ⁇ extruder (resin The temperature was 210 ° C.) and extruded into a strand from the tip of the extruder, and then granulated by cutting to produce polypropylene resin particles (1.2 mg / grain).
  • the dispersion was discharged under atmospheric pressure through a 3 mm ⁇ orifice provided at the lower part of the pressure vessel while maintaining the foaming pressure with the same gaseous substance as the foaming agent using No. 1 to obtain one-stage expanded particles. Then, it dried at 75 degreeC for 24 hours.
  • Examples 1 to 19 a polypropylene resin having a small amount of crystals having a crystal melting heat quantity of 50 J / g or more and less than 85 J / g is used. In Examples 20 to 23, a crystal melting heat quantity is 85 g / J or more and 95 g / g. A polypropylene resin having a large crystal content of J or less is used. From the results in Table 1, it can be understood that the in-mold foam-molded product according to the present invention has suppressed antistatic performance variation.
  • Example 22 which has a high foaming temperature of 168.0 ° C.
  • the average value of the surface specific resistance is 2 ⁇ 10 10 ⁇ or less
  • Examples 1 to 19 The results show that the antistatic performance is excellent when a polypropylene resin having a large amount of crystal is used.
  • Comparative Examples 1 to 13 As shown in Table 2, in Comparative Examples 1 to 13, the aliphatic diethanolamine fatty acid ester and the aliphatic diethanolamine were not used together or even if they were used together, the amount used was outside the range of the content of the present invention. . As can be seen from the results of the antistatic performance variation, the results of Comparative Examples 1 to 13 are clearly inferior to Examples 1 to 23, and the superiority of the present invention is clear. In particular, Comparative Examples 1 and 8 use the same amounts of glycerin stearic acid ester and polyethylene glycol, Comparative Example 1 uses a polypropylene resin with a small amount of crystal, and Comparative Example 8 uses a polypropylene resin with a large amount of crystal. Is used.
  • Comparative Example 1 the surface specific resistance average value is 3 ⁇ 10 12 ⁇ , and in Comparative Example 8, the surface specific resistance average value is 5 ⁇ 10 13 ⁇ .
  • the antistatic performance is inferior. This is contrary to the result of excellent antistatic performance when using a polypropylene resin with a large amount of crystal shown in Examples 20, 21, and 23, and the heterogeneous effect of the present invention is clearly shown. It can be said.
  • Examples 24 to 40, Comparative Examples 14 to 17 [Production of polypropylene resin particles]
  • the type and amount of polypropylene resin, antistatic agent, aliphatic alcohol, other additives shown in Table 3 or Table 4, and 0.01 parts by weight of the organic pigment perylene red are mixed and kneaded with a 50 mm ⁇ extruder (resin The temperature was 210 ° C.) and extruded into a strand from the tip of the extruder, and then granulated by cutting to produce polypropylene resin particles (1.2 mg / grain).
  • a 10 L pressure vessel is charged with 300 parts by weight of water, 100 parts by weight of the obtained polypropylene resin particles, 0.8 parts by weight of calcium triphosphate as a dispersant, and 0.03 parts by weight of normal paraffin sulfonate sodium as a dispersion aid. Further, the foaming agent of the type and amount shown in Table 3 or Table 4 was charged, and after stirring for 30 minutes at the foaming temperature (container temperature) and foaming pressure (container pressure) shown in Table 1, The dispersion was discharged under atmospheric pressure through a 3 mm ⁇ orifice provided at the lower part of the pressure vessel while maintaining the foaming pressure with the same gaseous substance as the foaming agent using No. 1 to obtain one-stage expanded particles. Then, it dried at 75 degreeC for 24 hours.
  • the first-stage expanded particles were each charged into a 1 m 3 pressure-resistant container and air-pressurized to give an internal pressure higher than normal pressure to the first-stage expanded particles. Subsequently, after transferring to a two-stage foaming machine, it was further foamed by heating with steam to obtain two-stage foamed particles. At this time, the foamed particle internal pressure and the water vapor pressure were set to the values shown in Table 3 or Table 4 (two-stage foaming conditions).
  • Examples 24 to 40 From the results of Examples 24 to 40, it is clear that the variation in surface specific resistance of the in-mold foam molded product according to the present invention is suppressed. Further, in Examples 38 to 40 using a polypropylene resin having a large amount of crystal, the average surface specific resistance is approximately the same as in Examples 24 to 37, and when a polypropylene resin having a large amount of crystal is used. The results are different from the general tendency that the surface resistivity average value is inferior to that of the polypropylene resin having a small amount of crystals.
  • Example 41 Comparative Example 18
  • the type and amount of polypropylene resin, antistatic agent, aliphatic alcohol, other additives, and 0.01 parts by weight of the organic pigment perylene red are mixed and kneaded in a 50 mm ⁇ extruder (resin temperature 210 ° C. And then extruded into a strand shape from the tip of the extruder and then granulated by cutting to produce polypropylene resin particles (1.2 mg / particle).
  • a 10 L pressure vessel is charged with 300 parts by weight of water, 100 parts by weight of the obtained polypropylene resin particles, 0.5 parts by weight of tribasic calcium phosphate as a dispersant, and 0.02 parts by weight of normal paraffin sulfonate sodium as a dispersion aid. Under stirring, the pressure vessel was set to the foaming temperature (inside vessel temperature) shown in Table 5, and further, the inside of the pressure vessel was pressurized with air to obtain the foaming pressure (inside vessel pressure) shown in Table 5 to 30.
  • the dispersion After holding for a minute and making it water-containing, the dispersion is discharged under a saturated water vapor pressure of 0.05 MPa (gauge pressure) through a 3 mm ⁇ orifice provided at the lower part of the pressure vessel while keeping the inside of the pressure vessel at the foaming pressure with air. First-stage expanded particles were obtained. Then, it dried at 75 degreeC for 24 hours.
  • the obtained first-stage expanded particles were charged into a 1 m 3 pressure-resistant container and air-pressurized to give an internal pressure higher than normal pressure to the first-stage expanded particles. Subsequently, after transferring to a two-stage foaming machine, it was further foamed by heating with steam to obtain two-stage foamed particles.
  • the foamed particle internal pressure and water vapor pressure at this time were set to the values shown in Table 5 (two-stage foaming conditions).
  • Example 42 [Production of polypropylene resin particles]
  • the type and amount of polypropylene resin, antistatic agent, aliphatic alcohol, other additives, and 0.01 parts by weight of the organic pigment perylene red are mixed and kneaded in a 50 mm ⁇ extruder (resin temperature 210 ° C. And then extruded into a strand shape from the tip of the extruder and then granulated by cutting to produce polypropylene resin particles (1.2 mg / particle).
  • a 10 L pressure vessel is charged with 300 parts by weight of water, 100 parts by weight of the obtained resin particles, 1.2 parts by weight of calcium triphosphate as a dispersing agent and 0.05 parts by weight of normal paraffin sulfonic acid soda as a dispersing aid, Then, 15 parts by weight of isobutane was charged, and the mixture was stirred for 30 minutes at the foaming temperature (container temperature) and foaming pressure (container pressure) shown in Table 5. Then, the pressure inside the pressure container was maintained at the foaming pressure with nitrogen. The aqueous dispersion was discharged under atmospheric pressure through a 5 mm ⁇ orifice provided at the bottom of the container to obtain single-stage expanded particles.

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Abstract

Le corps moulé en mousse dans le moule ci-décrit comprend des particules de mousse en résine polypropylène caractérisées en ce qu'elles comprennent une composition de résine polypropylène contenant un ester d'acide gras de diéthanolamine aliphatique et une diéthanolamine aliphatique, à raison d'un total de 0,1 à 5 parties en poids, limites comprises, d'ester d'acide gras de diéthanolamine aliphatique et de diéthanolamine aliphatique pour 100 parties en poids de résine polypropylène.
PCT/JP2013/057267 2012-03-14 2013-03-14 Particules de mousse en résine polypropylène, corps moulé en mousse dans le moule comprenant des particules de mousse en résine polypropylène, et procédé de production WO2013137411A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US14/384,590 US20150025162A1 (en) 2012-03-14 2013-03-14 Polypropylene resin foam particles, in-mold foam molded body comprising polypropylene resin foam particles, and method for producing same
EP13760551.5A EP2826813B1 (fr) 2012-03-14 2013-03-14 Particules de mousse en résine polypropylène, corps moulé en mousse dans le moule comprenant des particules de mousse en résine polypropylène, et procédé de production
CN201380014019.5A CN104245809B (zh) 2012-03-14 2013-03-14 聚丙烯系树脂发泡颗粒、由聚丙烯系树脂发泡颗粒而得的模内发泡成形体、以及它们的制造方法
JP2014505007A JP5976098B2 (ja) 2012-03-14 2013-03-14 ポリプロピレン系樹脂発泡粒子およびポリプロピレン系樹脂発泡粒子からなる型内発泡成形体、並びに、これらの製造方法

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JP2012-057141 2012-03-14
JP2012057141 2012-03-14

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WO2013137411A1 true WO2013137411A1 (fr) 2013-09-19

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US (1) US20150025162A1 (fr)
EP (1) EP2826813B1 (fr)
JP (1) JP5976098B2 (fr)
CN (1) CN104245809B (fr)
MY (1) MY165732A (fr)
WO (1) WO2013137411A1 (fr)

Cited By (6)

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JP2015081274A (ja) * 2013-10-22 2015-04-27 株式会社ジェイエスピー 帯電防止性複合樹脂発泡粒子の製造方法及び帯電防止性複合樹脂発泡粒子成形体
JP2017061624A (ja) * 2015-09-25 2017-03-30 株式会社ブリヂストン タイヤ
EP3190150A4 (fr) * 2014-08-21 2018-01-24 Kaneka Corporation Particules conductrices de mousse de résine à base de polypropylène excellentes en termes de propriétés antisalissure et d'aptitude au moulage, procédé de fabrication de particules de mousse de résine à base de polypropylène, et corps moulé de mousse de résine à base de polypropylène
WO2018190353A1 (fr) * 2017-04-14 2018-10-18 株式会社カネカ Particules expansées de résine de polypropylène ainsi que procédé de fabrication de celles-ci, et corps moulé par expansion de résine de polypropylène dans une matrice
US10385178B2 (en) 2014-01-17 2019-08-20 Jsp Corporation Propylene-based resin foam particle and foam particle molded body
US10487188B2 (en) * 2015-07-15 2019-11-26 Jsp Corporation Propylene resin foamed particle and foamed particle molded body

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US10882968B2 (en) 2016-08-30 2021-01-05 Lcy Chemical Corporation Polypropylene foams and processes of making

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JPH07304895A (ja) 1994-05-09 1995-11-21 Jsp Corp ポリプロピレン系樹脂発泡粒子及びその製造方法
JPH0812798A (ja) 1994-06-28 1996-01-16 Kanegafuchi Chem Ind Co Ltd 帯電防止性を有するポリオレフィン系樹脂予備発泡粒子およびその製法
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JP2000007854A (ja) 1998-06-26 2000-01-11 Kao Corp 帯電防止性樹脂組成物
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JP2002146113A (ja) 2000-11-08 2002-05-22 Grand Polymer Co Ltd ポリオレフィン樹脂組成物およびそのフィルム
JP2002179812A (ja) 2000-12-14 2002-06-26 Du Pont Mitsui Polychem Co Ltd 農業用フイルム
JP2003231770A (ja) 2002-02-08 2003-08-19 Jsp Corp 帯電防止ポリエステル系樹脂発泡粒子及びその成形体
WO2009001645A1 (fr) 2007-06-22 2008-12-31 Kaneka Corporation Particule préexpansée de résine de polyoléfine présentant des propriétés antistatiques et article moulé produit à partir de la particule
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015081274A (ja) * 2013-10-22 2015-04-27 株式会社ジェイエスピー 帯電防止性複合樹脂発泡粒子の製造方法及び帯電防止性複合樹脂発泡粒子成形体
US10385178B2 (en) 2014-01-17 2019-08-20 Jsp Corporation Propylene-based resin foam particle and foam particle molded body
EP3190150A4 (fr) * 2014-08-21 2018-01-24 Kaneka Corporation Particules conductrices de mousse de résine à base de polypropylène excellentes en termes de propriétés antisalissure et d'aptitude au moulage, procédé de fabrication de particules de mousse de résine à base de polypropylène, et corps moulé de mousse de résine à base de polypropylène
US10487188B2 (en) * 2015-07-15 2019-11-26 Jsp Corporation Propylene resin foamed particle and foamed particle molded body
JP2017061624A (ja) * 2015-09-25 2017-03-30 株式会社ブリヂストン タイヤ
US10946698B2 (en) 2015-09-25 2021-03-16 Bridgestone Corporation Tire
WO2018190353A1 (fr) * 2017-04-14 2018-10-18 株式会社カネカ Particules expansées de résine de polypropylène ainsi que procédé de fabrication de celles-ci, et corps moulé par expansion de résine de polypropylène dans une matrice
JPWO2018190353A1 (ja) * 2017-04-14 2020-02-27 株式会社カネカ ポリプロピレン系樹脂発泡粒子の製造方法、ポリプロピレン系樹脂発泡粒子およびポリプロピレン系樹脂型内発泡成形体
JP7082611B2 (ja) 2017-04-14 2022-06-08 株式会社カネカ ポリプロピレン系樹脂発泡粒子の製造方法、ポリプロピレン系樹脂発泡粒子およびポリプロピレン系樹脂型内発泡成形体

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EP2826813A4 (fr) 2015-10-14
MY165732A (en) 2018-04-20
JPWO2013137411A1 (ja) 2015-08-03
EP2826813B1 (fr) 2016-05-25
JP5976098B2 (ja) 2016-08-23
CN104245809A (zh) 2014-12-24
US20150025162A1 (en) 2015-01-22
EP2826813A1 (fr) 2015-01-21
CN104245809B (zh) 2016-05-04

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